CN104284919A - Quaternized polyethylenimines with a high ethoxylation degree - Google Patents

Abstract

The present invention relates to an ethoxylated polyethylenimine polymer comprising (1) a polyethyleneimine backbone, (2) a polyoxyethylene chain wherein thepolyoxyethylene chain has an average of 40 to 90 ethyleneoxide units per unit of NH in the polyethyleneimine backbone, (3) a quaternization degree of from 1% to less than 50%.

Description

Quaternized polyethyleneimine with high degree of ethoxylation

The present invention relates to an ethoxylated polyethyleneimine polymer, comprising (1) a polyethyleneimine backbone, (2) having an average of 40-90 ethoxylates by hydrogen atoms in each polyethyleneimine backbone NH unit (3) The degree of quaternization of the nitrogen atoms present in the polyethyleneimine skeleton is from 1% to less than 50%.

Surface cleaning using liquid detergents presents ongoing problems for consumers. Consumers who use liquid detergents as mild liquid dishwashing detergent compositions or hard surface cleaning compositions often notice surface imperfections such as residual soil, streaks, films and/or spots after washing. Furthermore, consumers prefer that cleaning compositions dry more quickly after the cleaning process. Accordingly, there remains a need for liquid cleaning compositions that not only clean hard surfaces, but also provide improved shine and fast drying.

It is an object of the present invention to provide polymers which are suitable as additives to cleaning compositions for hard surfaces and which provide improved gloss and fast drying benefits when used in soft dishwashing or hard surface cleaning.

The use of polyalkyleneimines in cleaning compositions is known. Traditionally, polyalkyleneimines have been used in laundry detergents to provide soil suspension benefits. Polyethylenimines have also been used in hard surface cleaning compositions to provide various benefits.

WO 2011/051646 discloses a method of treating hard surfaces to improve stain repellency, especially oily stain repellency, which method comprises applying to the surface a Compounds of polyamines.

WO 2010/020765 discloses the use of compositions comprising polyalkyleneimines and/or salts or derivatives thereof to prevent corrosion of non-metallic inorganic items during a washing or rinsing process.

US2007/0275868A1 mentions liquid detergent compositions comprising alkoxylated polyethyleneimines having 1 or 2 alkoxylation modifications per nitrogen atom. The degree of permanent quaternization can be 0-30% polyethyleneimine backbone nitrogen atoms.

WO 2006/108856 mentions amphiphilic water-soluble alkoxylated polyalkyleneimines comprising ethyleneoxy and propyleneoxy units and having a degree of quaternization of up to 50% for use as laundry detergents and cleaning compositions substance additives.

WO 2009/060059 describes amphiphilic water-soluble alkoxylated polyalkyleneimines comprising ethyleneoxy and propyleneoxy units for use as additives in laundry detergents.

It has surprisingly been found that the polymers of the present invention are not only effective in cleaning surfaces, but also provide improved gloss benefits when used in soft dishwashing or hard surface cleaning.

Ethoxylated polyethyleneimine polymer

The ethoxylated polyethyleneimines of the present invention have the general structure of formula (I):

Wherein n is the value of 40-90, the R of formula (I) is selected from hydrogen, C ₁ -C ₄ alkyl and mixtures thereof, E represents C ₁ -C ₁₂ alkyl moiety, X ^- represents a suitable water-soluble counterbalance The degree of quaternization of the ionic and nitrogen atoms present in the polyethyleneimine backbone is 1-50%, more preferably 5-40%, especially 15-30%. R is preferably a hydrogen atom. Quaternization is preferably achieved by reaction with dimethyl sulfate.

In a preferred embodiment, n has a value of 45-80, even more preferably 50-80.

In another preferred embodiment, the polyethyleneimine backbone has a weight average molecular weight of 400-10000 g/mol, more preferably 400-6000 g/mol, even more preferably 400-1800 g/mol.

Substitution of the ethyleneimine backbone includes: (1) 1 or 2 ethoxylation modifications per nitrogen atom, depending on whether the modification is at an internal or terminal nitrogen atom in the ethyleneimine backbone. Ethoxylation modification by hydrogen atoms are each modified with an average of about 40-90 ethoxy units, preferably about 45-80 ethoxy units, more preferably about 50-80 ethoxy units Oxyethylene chain displacement composition. Ethoxylation-modified terminal ethoxy units are blocked with hydrogen, C ₁ -C ₄ alkyl or mixtures thereof. (2) Quaternary tertiary nitrogen atoms with 0, 1 or 2 polyoxyethylene chains. Quaternization is preferably achieved by introducing C ₁ -C ₁₂ -alkyl, aryl or alkaryl groups and can be carried out in a customary manner by reaction with the corresponding alkyl halides, alkylaryl halides and dialkyl sulfates.

The degree of quaternization of nitrogen atoms present in the polyethyleneimine backbone is 1-50%, preferably 5-40%, most preferably 15-30% of the polyethyleneimine backbone nitrogen atoms.

For example, but without limitation, the following shows possible modifications to the terminal nitrogen atoms in the polyethyleneimine backbone, where R represents an ethylene spacer, E represents a C ₁ -C ₁₂ alkyl unit and X ^- represents a suitable Water-soluble counterions such as chlorine, bromine, and iodine, sulfate (i.e., -O-SO ₃ H or -O-SO ₃ ^- ), alkylsulfonates such as methylsulfonate, arylsulfonates such as tosylate , and alkylsulfates such as methylsulfate (ie -O- _SO2 -OMe).

Also for example, but not limited to, possible modifications to internal nitrogen atoms in the polyethyleneimine backbone are shown below, where R represents an ethylene spacer, E represents a C ₁ -C ₁₂ alkyl unit and X- represents Suitable water soluble counterions.

These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of catalysts such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, such as G. Scherr, U. Steuerle and R. Fikentscher: Kirk - "Cyclic imines" in Othmer Encyclopedia of Chemical Technology and "Aziridines" in U. Steuerle, R. Feuerhake: Ullmann's Encyclopedia of Industrial Chemistry.

The alkoxylated polyalkyleneimines according to the invention can be prepared in a known manner by reacting polyalkyleneimines with alkylene oxides. Suitable alkylene oxides are C ₂ -C ₂₀ alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, pentene oxide, hexene oxide, decylene oxide, dodecene oxide and the like. The polyalkyleneimine is reacted with a single alkylene oxide or a combination of two or more different alkylene oxides. The use of two or more alkylene oxides can give the resulting polymer a block-like structure or a random structure.

A preferred procedure consists first of all in a first step of carrying out only the initial alkoxylation of the polyalkyleneimine. In this step the polyalkyleneimines are reacted with only a fraction of the total amount of alkylene oxide used which corresponds to 1 mol of alkylene oxide per mole of NH moiety. The reaction is usually carried out in aqueous solution at a reaction temperature of about 70-200°C, preferably about 80-160°C, in the absence of a catalyst. The reaction can be carried out at a pressure of up to 10 bar, especially up to about 8 bar.

A further ethoxylation is then carried out in a second step by subsequent reaction with the remaining amount of ethylene oxide. This further ethoxylation is generally carried out in the presence of a basic catalyst. Examples of suitable catalysts are alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, especially sodium and potassium _C1 - _C4 alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Preference is given to alkali metal hydroxides and alkali metal alkoxides, particular preference to potassium hydroxide and sodium hydroxide. Typical amounts of the base used are from 0.05 to 10% by weight, especially from 0.5 to 2% by weight, based on the total amount of polyalkyleneimine and alkylene oxide.

This further ethoxylation can be carried out in bulk (Variant a)) or in an organic solvent (Variant b)). In variant a), the initially alkoxylated polyalkyleneimine aqueous solution obtained in the first step is first dehydrated after addition of the catalyst. This can be accomplished in a simple manner by heating to about 80-150° C. and distilling off the water under reduced pressure of about 0.01-0.5 bar. This subsequent reaction with ethylene oxide is generally carried out at a reaction temperature of about 70-200°C, preferably about 100-180°C. This subsequent reaction with alkylene oxide is generally carried out at a pressure of up to 10 bar, especially up to 8 bar. The reaction time for this subsequent reaction with alkylene oxide is generally about 0.5-4 hours.

Organic solvents suitable for variant b) are especially apolar and polar aprotic organic solvents. Examples of particularly suitable nonpolar aprotic solvents include aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, toluene and xylene. Examples of particularly suitable polar aprotic solvents are ethers, especially cyclic ethers such as tetrahydrofuran and dihydrofuran alkanes, N,N-dialkylamides such as dimethylformamide and dimethylacetamide, and N-alkyllactams such as N-methylpyrrolidone. It is of course also possible to use mixtures of these organic solvents. Preferred organic solvents are xylene and toluene.

In variant b), the solution obtained in the first step is first dehydrated after addition of catalyst and solvent, advantageously by separating off the water at a temperature of about 120-180° C., the separation being preferably supported by a gentle nitrogen flow . The subsequent reaction with alkylene oxides can be carried out as in scheme a). In variant a), the alkoxylated polyalkyleneimines are obtained directly in bulk and can, if desired, be converted into aqueous solutions. In variant b), the organic solvent is generally removed and replaced with water. The products can of course also be isolated in bulk.

The quaternization of alkoxylated polyethyleneimines is preferably achieved by introducing C ₁ -C ₁₂ alkyl, aryl or alkylaryl groups and can be achieved by reacting with the corresponding alkyl halides, alkylaryl halides and dialkyl sulfates. The ester reaction is carried out in a conventional manner, for example as described in WO 2009060059.

The quaternization of ethoxylated polyethyleneimines is preferably achieved by reacting the amine with at least one alkylating compound selected from the group of compounds of the formula EX, where E is _C1 - _C12 alkyl, aryl or alkyl Aryl and X is a leaving group capable of being displaced by nitrogen (and C ₂ -C ₆ alkylene oxides, especially ethylene oxide or propylene oxide).

Suitable leaving groups X are halogen, especially chlorine, bromine or iodine, sulfate (ie -OSO ₃ H or -OSO ₃ ^- ), alkylsulfonate such as methylsulfonate, arylsulfonate such as tolyl Sulfonate, and alkylsulfate such as methylsulfate (ie _-OSO2OMe ). Preferred alkylating agents EX are C ₁ -C ₁₂ alkyl halides, di(C ₁ -C ₁₂ alkyl)sulfates and benzyl halides. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, benzyl chloride, dimethyl sulfate, diethyl sulfate.

The amount of alkylating agent determines the amount of quaternization of amino groups in the polymer, ie the amount of quaternization moieties.

The amount of quaternized moiety can be calculated from the difference in the amine values of the unquaternized amine and the quaternized amine.

The amine value can be determined according to the method described in DIN 16945.

This reaction can be performed without any solvent. However, solvents or diluents such as water, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone and the like may be used. The reaction temperature is usually 10-150°C, preferably 50-110°C.

For the purposes of the present invention, "consisting essentially of" is understood to mean that the copolymer of the present invention may contain a certain amount of impurities or other oxyalkylene groups other than ethylene oxide. Thus, the polymers of the invention may contain up to 5 alkylene oxide groups other than ethylene oxide, such as propylene oxide or butylene oxide, per mole of NH in the polyethyleneimine backbone.

Compositions comprising ethoxylated polyethyleneimine polymers of the present invention

The ethoxylated polyethyleneimine polymers of the present invention may be included in hard surface cleaning detergent compositions, hand dishwashing detergent composition or automatic dishwashing detergent composition.

Compositions comprising the ethoxylated polyethyleneimine polymers of the present invention may be in a form selected from liquids, gels and solids. Preferably the compositions comprising the polymers of the invention are liquid or gel cleaning compositions.

The ethoxylated polyethyleneimine polymers according to the invention may also be involved in technical chemical applications, car washing, cosmetics, paper and cardboard manufacture, leather and the textile industry.

In a preferred embodiment, the hard surface cleaning compositions comprising the ethoxylated polyalkyleneimine polymers of the present invention are used to provide fast drying and/or to provide shine on household hard surfaces. In an alternative preferred embodiment, hand dishwashing detergent compositions comprising the polymers of the present invention are used to provide fast drying and/or to provide shine on pots, dishes, glassware, cutlery and the like in hand dishwashing cleaning operations. In another preferred embodiment, automatic dishwashing compositions comprising the polymers of the present invention are used to provide fast drying and/or to provide shine on pots, dishes, glassware, cutlery, etc. in automatic dishwashing operations.

In a preferred embodiment, the composition is a hard surface cleaning composition comprising about 70-99% by weight of the entire composition, preferably about 75-95% by weight, more preferably about 80-95% by weight of water .

Alternatively, in another preferred embodiment, the composition is a hand dishwashing detergent composition comprising about 30-95% by weight of the entire composition, preferably about 40-80% by weight, more preferably about 50-75% by weight % by weight of water.

In preferred embodiments wherein the composition is a hard surface cleaning composition, the composition has a pH of about 2-14, preferably about 2-10, more preferably about 2-9.5, even more preferably about 2.1-8, which Measured at 25°C. In preferred embodiments wherein the composition is a hand dishwashing detergent composition, the composition has a pH of about 3-14, preferably about 6-13, most preferably about 8-11.

The hard surface cleaning composition, the hand dishwashing detergent composition and the automatic dishwashing composition - all comprising the ethoxylated polyalkyleneimine polymers of the present invention and used to provide fast drying and/or household hard surface cleaning compositions. Provides gloss on the surface - may contain the following additional ingredients:

Surfactant

Surfactants may be present in amounts of 0-15% by weight of the total composition, preferably 0.1-10% by weight, most preferably 0.25-8% by weight.

Surfactants may be desirable herein as they contribute to the cleaning performance of the liquid cleaning compositions of the present invention. Suitable surfactants are selected from nonionic surfactants or mixtures thereof; anionic surfactants or mixtures thereof; amphoteric surfactants or mixtures thereof; zwitterionic surfactants or mixtures thereof; cationic surfactants or mixtures thereof; their mixture.

In preferred embodiments wherein the composition is a hard surface cleaning composition, the composition comprises about 1-60% by weight of the total composition, preferably about 5-30% by weight, more preferably about 10-25% by weight surface active agent.

In preferred embodiments wherein the composition is a hand dishwashing detergent composition, the composition may comprise about 5-80% by weight of the entire composition, preferably about 10-60% by weight, more preferably about 12-45% by weight of surfactants. In preferred embodiments, the surfactants herein have an average alkyl chain branching of greater than about 10% by weight of the total surfactant, preferably greater than about 20% by weight, more preferably greater than about 30% by weight, even more preferably greater than About 40% by weight.

nonionic surfactant

In a preferred embodiment, the liquid cleansing composition comprises a nonionic surfactant. Suitable nonionic surfactants may be alkoxylated alcohol nonionic surfactants, which may be readily produced by condensation methods well known in the art.

Accordingly, preferred alkoxylated alcohols for use herein are nonionic surfactants of the formula R ¹ O(E) _e (P) _p H, wherein R ¹ is a hydrocarbon chain having from about 2 to 24 carbon atoms, E is ethylene oxide, P is propylene oxide and e and p, representing the average degree of ethoxylation and propoxylation, respectively, range from about 0 to 24 (the sum of e+p is at least 1). Preferably the hydrophobic moiety of the nonionic compound may be a linear or branched primary or secondary alcohol having from about 8 to 24 carbon atoms.

Preferably the nonionic surfactant is included in typical amounts of about 2-40%, preferably about 3-30%, preferably about 3-20% by weight of the liquid cleansing composition, by weight of the total composition.

Also suitable are alkyl polyglycosides of formula R ³ O(C _n H _2n O) _t (glycosyl) _z (formula (III)), wherein R ³ of formula (III) is selected from alkyl groups or mixtures thereof; Alkylphenyl or mixtures thereof; Hydroxyalkylphenyl or mixtures thereof; Hydroxyalkylphenyl or mixtures thereof; and mixtures thereof, wherein the alkyl group contains about 10-18, preferably about 12-14 carbon atoms; the formula ( n of III) is about 2 or about 3, preferably about 2; t of formula (III) is about 0-10, preferably about 0; and z of formula (III) is about 1.3-10, preferably about 1.3-3, Most preferably about 1.3-2.7. The glycosyl is preferably derived from glucose. Also suitable are alkyl glyceryl ethers and sorbitan esters.

Also suitable are fatty acid amide surfactants of formula (IV):

Wherein formula (IV) R ⁶ is an alkyl group containing about 7-21, preferably about 9-17 carbon atoms, and each R ⁷ of formula (IV) is selected from hydrogen; C ₁ -C ₄ alkyl or mixtures; C ₁ -C ₄ hydroxyalkyl groups or mixtures thereof; and -(C ₂ H ₄ O) _y H or mixtures thereof, wherein y of formula (IV) is about 1-3. Preferred amides may be C ₈ -C ₂₀ aminoamides, monoethanolamides, diethanolamides and isopropanolamides.

In a preferred embodiment, the weight ratio of total surfactant to nonionic surfactant is about 2-10, preferably about 2-7.5, more preferably about 2-6.

anionic surfactant

Anionic surfactants suitable for use in the liquid cleaning composition may be sulfates, sulfosuccinates, sulfoacetates and/or sulfonates; preferably alkyl sulfates and/or alkyl ethoxylates Sulfates; more preferably combinations of alkyl sulfates and/or alkyl ethoxy sulfates having a combined degree of ethoxylation of less than about 5, preferably less than about 3, more preferably less than about 2.

Sulfate or sulfonate surfactants are usually present in an amount of at least about 5% by weight, preferably about 5-40% by weight, more preferably about 15-30% by weight, even more preferably about 15-25% by weight, of the liquid cleaning composition. concentration exists.

Sulfate or sulphonate surfactants suitable for use in the liquid cleansing compositions include the water-soluble salts or acids of _C8 - _C14 alkyl or hydroxyalkyl sulfuric or sulphonic acids. Suitable counterions include hydrogen, alkali metal cations or ammonium or substituted ammonium, but sodium is preferred. When the hydrocarbyl chain is branched, it preferably comprises C _1-4 alkyl branching units. The average percent branching of the sulfate or sulfonate surface activity is preferably greater than about 30% of the total hydrocarbon chain, more preferably about 35-80%, most preferably about 40-60%.

The sulfate or sulfonate surfactants may be selected from C ₁₁ -C ₁₈ alkylbenzene sulfonates (LAS), C ₈ -C ₂₀ branched and random primary alkyl sulfates (AS); C ₁₀ - C ₁₈ secondary (2,3) alkyl sulfate; C ₁₀ -C ₁₈ alkyl alkoxy sulfate (AE _x S), where x is preferably 1-30; preferably contains about 1-5 ethoxy units C ₁₀ -C ₁₈ alkyl alkoxy carboxylates; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl as discussed in US 6,008,181 and US 6,020,303 Alkoxysulfates; eg WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549 and WO 00/ Modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS) discussed in 23548.

The paraffin sulfonates may be paraffin mono- or disulfonates and generally mixtures thereof, which are obtained by sulfonating paraffins having about 10 to 20 carbon atoms. Preferred sulfonates are those having a chain of C _12-18 carbon atoms, more preferably they are a C _14-17 chain.

Also suitable are alkyl glyceryl sulfonate surfactants and/or alkyl glyceryl sulfate surfactants. A mixture of oligomeric alkylglyceryl sulfonate and/or sulfate surfactants selected from the group consisting of dimers or mixtures thereof; trimers or mixtures thereof; tetramers or mixtures thereof; pentamers or mixtures thereof mixtures; hexamers or mixtures thereof; heptamers or mixtures thereof; and mixtures thereof; wherein the alkylglyceryl sulfonate and/or sulfate surfactant mixture comprises about 0-60% by weight monomer.

Further suitable anionic surfactants are alkyl, preferably dialkyl sulfosuccinates and/or sulfoacetates. The dialkyl sulfosuccinate may be _diC6-15 linear or branched alkyl sulfosuccinate. The alkyl moieties may be symmetric (ie, the same alkyl moiety) or asymmetric (ie, different alkyl moieties). Preferably the alkyl moiety is symmetrical.

The most common branched anionic alkyl ether sulfates are obtained via sulfation of mixtures of branched alcohols and branched alcohol ethoxylates. Also suitable are sulfated fatty alcohols derived from the Fischer & Tropsh reaction containing up to 50% branching (about 40% methyl (mono or di), about 10% cyclohexyl), such as those produced from Safol alcohol from Sasol; Sulfated fatty alcohols derived from oxo reactions, wherein at least about 50% by weight of the alcohols are _C2 isomers (methyl to pentyl), as obtained from Sasol Alcohol or Those produced from alcohols; sulfated fatty alcohols derived from modified oxo reactions, wherein at least about 15% by weight of the alcohol is the _C2 isomer (methyl to pentyl), as obtained from Shell those produced by alcohol.

Zwitterionic Surfactants and Amphoteric Surfactants

Zwitterionic and amphoteric surfactants for use in the liquid cleaning composition may be included at a concentration of about 0.01-20%, preferably about 0.2-15%, more preferably about 0.5-10% by weight of the hand dishwashing detergent composition .

Suitable zwitterionic surfactants in a preferred embodiment contain both basic and acidic groups which form internal salts giving both cationic and anionic hydrophilic groups on the same molecule over a wide pH range. A typical cationic group is a quaternary ammonium group, but other positively charged groups such as , imidazole and sulfonium groups. Typical anionic hydrophilic groups are carboxylate and sulfonate, but other groups such as sulfate, phosphonate, etc. can be used.

The liquid cleaning composition may preferably further comprise amine oxides and/or betaines. The most preferred amine oxide is cocodimethylamine oxide or cocamidopropyldimethylamine oxide. Amine oxides can have linear or moderately branched alkyl moieties. Typical linear amine oxides include one R ⁴ C _8-18 alkyl moiety and two R ⁵ and R ⁸ selected from C _1-3 alkyl and mixtures thereof and C _1-3 hydroxyalkyl and mixtures thereof Water-soluble amine oxides of structural moieties. Preferred amine oxides are characterized by the formula R ⁴ —N(R ⁵ )(R ⁸ )→O, wherein R ⁴ is C _8-18 alkyl and R ⁵ and R ⁸ are selected from methyl, ethyl, propyl, iso Propyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants may include linear C ₁₀ -C ₁₈ alkyl dimethylamine oxides and linear C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides, among others. Preferred linear amine oxides include linear C ₁₀ , linear C ₁₀ -C ₁₂ and linear C ₁₂ -C ₁₄ alkyl dimethylamine oxides.

As used herein, "moderately branched" means that the amine oxide has an alkyl moiety having n ₁ carbon atoms and an alkyl branch having n ₂ carbon atoms on the alkyl moiety. The alkyl branch is located on the carbon alpha to the nitrogen on the alkyl moiety. This type of branching of the amine oxides is also known in the art as internal amine oxides. The sum of _n1 and _n2 is about 10-24, preferably about 12-20, more preferably about 10-16 carbon atoms. The one alkyl moiety (n ₁ ) should have approximately the same number of carbon atoms as the one alkyl branch (n ₂ ) such that the one alkyl moiety and the one alkyl branch are symmetrical. "Symmetric" as used herein means that | _n1 - _n2 | is less than or equal to 5, preferably about 4, in at least about 50% by weight, more preferably at least about 75-100% by weight of the moderately branched amine oxides used herein , most preferably about 0-4 carbon atoms.

The amine oxide further comprises two moieties independently selected from the group consisting of C _1-3 alkyl, C _1-3 hydroxyalkyl, or polyoxyethylene groups containing an average of about 1-3 ethylene oxide groups. Preferably the two moieties are selected from C _1-3 alkyl groups, more preferably both are selected from C ₁ alkyl groups.

Other suitable surfactants include betaines such as alkyl betaines, alkyl amido betaines, amido azoles Betaine (amidazoliniumbetaine), sulphobetaine (INCI sultaine), and phosphobetaine (phosphobetaine), and preferably satisfy the formula I:

R ^1' -[CO-X(CH ₂ ) _j ] _g -N ⁺ (R ^2' )(R ^3' )-(CH ₂ ) _f -[CH(OH)-CH ₂ ] _h -Y-(I )

in

R ^1' is a saturated or unsaturated C _6-22 alkyl group, preferably a C _8-18 alkyl group, especially a saturated C _10-16 alkyl group, such as a saturated C _12-14 alkyl group;

X is NH, NR ^4' with C _1-4 alkyl R ^4' , O or S,

j is about 1-10, preferably about 2-5, especially about 3,

g is about 0 or about 1, preferably about 1,

R ^2' and R ^3' are independently C _1-4 alkyl, substituted potential hydroxyl such as hydroxyethyl, preferably substituted by methyl,

f is a number of about 1-4, especially about 1, 2 or 3,

h is approximately 0 or 1, and

Y is selected from COO, SO ₃ , OPO(OR ^5′ )O or P(O)(OR ^5′ )O, wherein R ^5′ is a hydrogen atom H or a C _1-4 alkyl group.

Preferred betaines are alkyl betaines of formula (I _a ), alkyl amido betaines of formula (I _b ), sulphobetaines of formula (I _c ) and sulfobetaines of formula (I _d ). Amino sulfobetaine:

R ^1' -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (I _a )

R ^1' -CO-NH(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (I _b )

R ^1' -N ⁺ (CH ₃ ) ₂ -CH ₂ CH(OH)CH ₂ SO ₃ ^- (I _c )

R ^1' -CO-NH-(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH(OH)CH ₂ SO ₃ ^- (I _d )

wherein R ^1' has the same meaning as in formula I. Particularly preferred betaines are carbonyl betaines, wherein Y ^- is [COO ^- ], especially carbonyl betaines of formula (I _a ) and (I _b ), more preferably alkylamides of formula (I _b ) base betaine.

Examples of suitable betaines and sulphobetaines are those (according to INCI): apricot oleamidopropyl betaine, apricot oleamidopropyl betaine, avocado oleamidopropyl betaine, Babassu Oleamidopropyl Betaine, Behenylamidopropyl Betaine, Behenyl Betaine, Betaine, Low Erucicamidopropyl Betaine, Caprylyl/Capricamidopropyl Betaine Betaine, Carnitine, Cetyl Betaine, Cocamidoethyl Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco Betaine, Coco Hydroxysultaine, Cocoyl/Oleamidopropyl Betaine, Coco Sultaine, Decyl Betaine, Oleyl Glycine Dihydroxyethyl Ester, Soybean Glycine Dihydroxyethyl Esters, Dihydroxyethyl Stearyl Glycine, Dihydroxyethyl Tallow Glycine, Dimethicone Propyl PG-Betaine, Drucamidopropylhydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauryl Amidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milk Amidopropyl Betaine, Milk Amidopropyl Betaine, Meat Myristylamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine, Oleyl Betaine, Oleamidopropyl Betaine, Palmitamide Propyl Betaine, Palm Oleamidopropyl Betaine, Palmitoyl Carnitine, Palm Kernel Amidopropyl Betaine, Teflon Acetoxypropyl Betaine, Ricinoleamidopropyl Betaine Ammonium Salt, Sesamemidopropyl Betaine, Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysulfo Betaine, tallow betaine, tallow dihydroxyethyl betaine, undecyl amidopropyl betaine and wheat germ amidopropyl betaine. A preferred betaine is eg cocamidopropyl betaine.

A particularly preferred zwitterionic surfactant for use in preferred embodiments wherein the composition is a hard surface cleaning composition is a sulphobetaine surfactant because it provides the best soap scum cleaning benefits.

Examples of particularly suitable sulphobetaine surfactants include tallow bis(hydroxyethyl) sulphobetaine and cocamidopropyl hydroxysulphobetaine.

cationic surfactant

In a preferred embodiment, the liquid cleansing composition may comprise cationic surfactant present in an effective amount, more preferably from about 0.1 to 20% by weight of the liquid cleansing composition. Suitable cationic surfactants are quaternary ammonium surfactants. Suitable quaternary ammonium surfactants are selected from N-mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ alkyl or alkenyl ammonium surfactants or mixtures thereof, wherein the remaining N positions are replaced by methyl, hydroxyethyl Or hydroxypropyl substitution. Another preferred cationic surfactant is a C ₆ -C ₁₈ alkyl or alkenyl ester of a quaternary ammonium alcohol, such as a quat. More preferably the cationic surfactant has formula (V):

Wherein formula (V) R ⁹ is C ₈ -C ₁₈ hydrocarbyl or mixture thereof, preferably C _8-14 alkyl, more preferably C ₈ , C ₁₀ or C ₁₂ alkyl; and Z of formula (V) is an anion, Chloride or bromide is preferred.

optional ingredients

The liquid cleaning compositions of the present invention may contain various optional ingredients depending on the technical benefit sought and the surface to be treated.

Optional ingredients suitable for use herein include alkaline materials or mixtures thereof; inorganic or organic acids and salts or mixtures thereof; buffers or mixtures thereof; surface modifying polymers or mixtures thereof; cleaning polymers or mixtures thereof; Oxygen bleaches or mixtures thereof; radical scavengers or mixtures thereof; chelating agents or mixtures thereof; perfumes or mixtures thereof; dyes or mixtures thereof; hydrotropes or mixtures thereof; polymeric foam stabilizers or mixtures thereof; diamines or mixtures thereof; and mixtures thereof.

solvent

Solvents are generally used to ensure product quality preferred for solubility, consistency and aesthetics and to ensure better processing. The liquid cleaning compositions of the present invention may further comprise solvents or mixtures thereof as optional ingredients. In general, in preferred embodiments wherein the composition is a hard surface cleaning composition, the composition may comprise from about 0.1 to 10% by weight of the total composition, preferably from about 0.5 to 5% by weight, more preferably from about 1 - 3% by weight of solvents or mixtures thereof. In preferred embodiments wherein the composition is a hand dishwashing detergent composition, the composition contains from about 0.01 to 20%, preferably from about 0.5 to 20%, more preferably from about 1 to 10%, by weight solvent.

Suitable solvents herein include _C1 - _C5 alcohols of formula ^R10 -OH, wherein ^R10 is a saturated alkyl group having about 1-5, preferably about 2-4 carbon atoms. Suitable alcohols are ethanol, propanol, isopropanol or mixtures thereof. Other suitable alcohols are alkoxylated C _1-8 alcohols of formula R ¹¹ —(A _q )—OH, wherein R ¹¹ is an alkyl group having about 1 to 8, preferably about 3 to 6 carbon atoms and wherein A is alkoxy, preferably propoxy and/or ethoxy and q is an integer of 1-5, preferably 1-2. Suitable alcohols are butoxypropoxypropanol (n-BPP), butoxypropanol (n-BP), butoxyethanol or mixtures thereof. Alkoxylated aromatic alcohols suitable for use herein are those of the formula R ¹² -(B) _r -OH, wherein R ¹² has about 1-20, preferably about 2-15, more preferably about 2- Alkyl-substituted or non-alkyl-substituted aryl with 10 carbon atoms, wherein B is alkoxy, preferably butoxy, propoxy and/or ethoxy, and r is 1-5, preferably 1-2 an integer of . A suitable aromatic alcohol for use herein is benzyl alcohol. Suitable alkoxylated aromatic alcohols are benzyl ethanol and/or benzyl propanol. Other suitable solvents include diethylene glycol butyl ether, benzyl alcohol, propoxypropoxypropanol (EP 0 859 044), ethers and diethers, glycols, alkoxylated glycols, C ₆ -C ₁₆ Glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C ₁ -C ₅ alcohols, linear C ₁ -C ₅ alcohols Alcohols, amines, C ₈ -C ₁₄ alkyl and cycloalkyl hydrocarbons and halogenated hydrocarbons, and mixtures thereof.

spices

The liquid cleansing compositions of the present invention may comprise a perfume ingredient, or mixtures thereof, in an amount of up to 5.0% by weight of the total composition, preferably from about 0.1 to 1.5% by weight. Perfume compounds and compositions suitable for use herein are for example those described on page 13 of EP-A-0957156 under the paragraph entitled "Perfume".

dye

The liquid cleaning compositions of the present invention can be pigmented. Therefore, it may contain dyes or mixtures thereof. Dyes suitable for use herein are acid stable dyes. "Acid stable" herein refers to compounds that are chemically and physically stable in the acidic environment of the compositions herein.

pH regulator

alkaline substance

Alkaline substances may preferably be present to adjust the pH and/or maintain the pH of the compositions of the invention. The amount of alkaline material is about 0.001-20% by weight of the composition, preferably about 0.01-10% by weight, more preferably about 0.05-3% by weight.

Examples of alkaline substances are sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or alkali metal oxides, such as sodium oxide and/or potassium oxide, or mixtures thereof. Preferably the source of alkalinity is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.

acid

The liquid cleaning compositions of the present invention may contain acids. Any acid known to the person skilled in the art can be used here. The compositions herein may generally comprise up to 20% by weight of the total composition, preferably about 0.1-10% by weight, more preferably about 0.1-5% by weight, even more preferably about 0.1-3% by weight of acid.

Suitable acids are selected from mono- and polycarboxylic acids or mixtures thereof; percarboxylic acids or mixtures thereof; substituted carboxylic acids or mixtures thereof; and mixtures thereof. Carboxylic acids useful herein include C _1-6 linear acids or cyclic acids containing at least 3 carbons. The linear or cyclic carbon-containing chain of the carboxylic acid may be substituted with substituents selected from hydroxyl, ester, ether, aliphatic groups having about 1-6, more preferably about 1-4 carbon atoms, and mixtures thereof.

Suitable mono- and polycarboxylic acids are selected from citric acid, lactic acid, ascorbic acid, erythorbic acid, tartaric acid, formic acid, maleic acid, malic acid, malonic acid, propionic acid, acetic acid, dehydroacetic acid, benzoic acid, hydroxybenzoic acid and mixtures thereof.

Suitable percarboxylic acids are selected from peracetic acid, percarbonic acid, perboric acid and mixtures thereof.

Suitable substituted carboxylic acids are selected from amino acids or mixtures thereof; halogenated carboxylic acids or mixtures thereof; and mixtures thereof.

Preferred acids for use herein are selected from lactic acid, citric acid and ascorbic acid and mixtures thereof. More preferred acids for use herein are selected from lactic acid and citric acid and mixtures thereof. An even more preferred acid for use herein is lactic acid.

Salt

In preferred embodiments, the liquid cleaning compositions of the present invention also include other salts as pH buffering agents. Salts are generally present at an active concentration of about 0.01-5%, preferably about 0.015-3%, more preferably about 0.025-2.0% by weight of the composition.

When salts are included, the ions may be selected from magnesium, sodium, potassium, calcium and/or magnesium, preferably sodium and magnesium, and as hydroxide, chloride, acetate, sulfate, formate, oxide or nitric acid Salts are added to the compositions of the present invention.

diamine

In another preferred embodiment, the liquid cleaning compositions according to the invention comprise diamines or mixtures thereof as pH buffering agents. The composition preferably contains about 0-15% by weight of the entire composition, preferably about 0.1-15% by weight, preferably about 0.2-10% by weight, more preferably about 0.25-6% by weight, more preferably about 0.5-1.5% by weight at least one diamine.

Preferred organic diamines are those wherein the pK ₁ and pK ₂ are about 8.0-11.5, preferably about 8.4-11, even more preferably about 8.6-10.75. Preferred materials include 1,3-bis(methylamine)cyclohexane (pKa = about 10-10.5), 1,3-propanediamine (pK ₁ =10.5; pK ₂ =8.8), 1,6-hexane Diamine (pK ₁ =11; pK ₂ =10), 1,3-pentanediamine (DYTEK ) (pK ₁ =10.5; pK ₂ =8.9), 2-methyl-1,5-pentanediamine (DYTEK ) (pK ₁ =11.2; pK ₂ =10.0). Other preferred materials include primary/primary diamines with _C4 - _C8 alkylene spacers. It is generally believed that primary diamines are preferred over secondary and tertiary diamines. pKa is used herein in the same way as is generally known to those skilled in the art of chemistry: a value of about 0.1-0.5M in full aqueous solution at 25°C and an ionic strength. References may be taken from literature such as "Critical Stability Constants: Volume 2, Amines", Smith and Martel, Plenum Press, NY and London, 1975.

Chelating agent

It has been found that the addition of chelating agents to liquid cleaning compositions of the present invention provides surprising improvements in their cleaning performance. In a preferred embodiment, the compositions of the present invention may comprise from about 0.1 to 20% by weight of the total composition, preferably from about 0.2 to 5%, more preferably from about 0.2 to 3% by weight of a chelating agent.

Suitable chelating agents may be selected from amino carboxylates or mixtures thereof; amino phosphonates or mixtures thereof; polyfunctionally substituted aromatic chelating agents or mixtures thereof; and mixtures thereof.

Chelating agents preferably used herein are amino acid-based chelating agents, preferably glutamic acid-N,N-diacetic acid (GLDA) and derivatives, and/or phosphonate-based chelating agents, and preferably diethylenetriaminepentamethene base phosphonic acid. GLDA (salts and derivatives thereof) is especially preferred according to the invention, and its tetrasodium salt is especially preferred.

Amino carboxylates are also preferred, including ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine Hexaacetate, diethylenetriaminepentaacetate, ethanol diglycine; their alkali metal, ammonium, and substituted ammonium salts; and mixtures thereof; also MGDA (methylglycine diacetic acid), and its salts and derivatives;

Other chelating agents include homopolymers and copolymers of polycarboxylic acids and their partially or fully neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts. Preferred salts of the abovementioned compounds are ammonium and/or alkali metal salts, ie lithium, sodium and potassium salts, particularly preferred salts are sodium salts.

Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, in which case they contain at least about 2 carboxyl groups separated from one another by preferably not more than about 2 carbon atoms in each case. Polycarboxylates containing two carboxy groups include, for example, the water-soluble salts of malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, hydroxymalonic acid and fumaric acid. Polycarboxylates containing 3 carboxyl groups include, for example, water-soluble citrates. Correspondingly, a suitable hydroxycarboxylic acid is, for example, citric acid. Another suitable polycarboxylic acid is a homopolymer of acrylic acid. Polycarboxylates terminated with sulfonate groups are preferred.

Other polycarboxylate chelating agents suitable for use herein include acetic acid, succinic acid, formic acid; all of which are preferably in the form of water-soluble salts. Other suitable polycarboxylates are oxydisuccinates, carboxymethyloxysuccinates and mixtures of tartrate monosuccinate and tartrate disuccinate as described in US 4,663,071.

Amino phosphonates are also suitable as chelating agents and include ethylenediaminetetrakis (methylene phosphonate) as DEQUEST. Preferably these amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents can also be used in the compositions herein, as described in US Patent No. 3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Hydrotrope

The liquid cleaning compositions of the present invention may optionally contain a hydrotrope in an amount effective to render the composition properly compatible in water. The compositions of the present invention generally comprise from about 0 to 15%, preferably from about 1 to 10%, most preferably from about 3 to 6%, by weight of the total composition of a hydrotrope or mixtures thereof. Hydrotropes suitable for use herein include anionic hydrotropes, especially sodium, potassium and ammonium xylene sulfonates, sodium, potassium and ammonium toluene sulfonates, sodium, potassium and ammonium cumene sulfonates, and mixtures thereof, and related compounds as described in US Patent 3,915,903.

Polymer Foam Stabilizer

The liquid cleaning compositions of the present invention may optionally contain polymeric suds stabilizers. These polymeric suds stabilizers provide extended suds volume and suds duration to the composition. The compositions preferably contain from about 0.01% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1% to about 5% by weight of the total composition of the polymeric foam booster/stabilizer.

These polymeric foam stabilizers may be selected from homopolymers of (N,N-dialkylamino)alkyl esters and (N,N-dialkylamino)alkyl acrylates. The polymeric suds booster has a weight average molecular weight as determined via conventional gel permeation chromatography of about 1,000-2,000,000, preferably about 5,000-1,000,000, more preferably about 10,000-750,000, more preferably about 20,000-500,000, even more preferably about 35,000 -200,000. The polymeric foam stabilizer may optionally be present in the form of a salt—inorganic or organic—for example citrate, sulfate or nitrate of (N,N-dimethylamino)alkylacrylate.

A preferred polymeric foam stabilizer is (N,N-dimethylamino) alkyl acrylate, acrylate shown in formula (VII):

Other preferred suds boosting polymers are hydroxypropyl acrylate/dimethylaminoethyl methacrylate copolymers (HPA/DMAM copolymers) of formulas VIII and IX:

Another preferred class of suds booster polymers are hydrophobically modified cellulosic polymers having a weight average molecular weight ( _Mw ) of less than about 45,000, preferably about 10,000-40,000, more preferably about 13,000-25,000. Hydrophobically modified cellulosic polymers include water-soluble cellulose ether derivatives, such as nonionic and cationic cellulose derivatives. Preferred cellulose derivatives include methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose and mixtures thereof.

Example

Synthetic example

The amount of alkylating agent determines the amount of quaternization of amino groups in the polymer, ie the amount of quaternization moieties.

The amount of quaternized moiety can be calculated from the difference in amine value in the unquaternized amine and the quaternized amine.

The amine value can be determined according to the method described in DIN 16945.

Embodiment 1: Synthesis of 25% quaternized PEI600EO40

a)PEI600+1EO/NH

1328.5 g of polyethyleneimine 600 (average molecular weight _Mw of 600) and 66.4 g of water were heated to 80° C. and purged 3 times with nitrogen to a pressure of 5 bar in a 3.5 L autoclave. After warming up to 120° C., 1359.4 g of ethylene oxide were added portionwise to 7 bar. To complete the reaction, the mixture was post-reacted at 120° C. for 2 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 70°C. The temperature was raised to 90-110°C and the mixture was dehydrated under vacuum for 2 hours.

2688 g of polyethyleneimine 600 with 1 mole of ethylene oxide per mole of NH was obtained as a yellow viscous oil (amine value: 549 mg KOH/g; pH of 1% by weight aqueous solution: 11.06).

b)PEI600+10EO/NH

704.5 g of the product obtained in Example 1 a) and 21.1 g of a 50% by weight aqueous potassium hydroxide solution were heated to 80° C. in a 5 L autoclave and purged 3 times with nitrogen. The mixture was dehydrated for 2 hours at 120° C. and a vacuum of 10 mbar. After the vacuum was removed with nitrogen, the temperature was raised to 145° C. and 3206.7 g of ethylene oxide were added portionwise to 7 bar. To complete the reaction, the mixture was post-reacted at 120° C. for 2 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 70°C.

3968 g of polyethyleneimine 600 having 10 mol ethylene oxide/mol NH bonds (amine value: 101.5 mg KOH/g; pH of 10% by weight aqueous solution: 11.6) were obtained as a yellow-brown viscous liquid.

c)PEI600+40EO/NH

1084.6 g of the product obtained in example 1 b) were heated to 80° C. in a 5 L autoclave and purged 3 times with nitrogen. The mixture was dehydrated at 120° C. and a vacuum of 10 mbar for 0.5 hours. After the vacuum was removed with nitrogen, the temperature was raised to 145° C. and 2927.6 g of ethylene oxide were added portionwise to 7 bar. To complete the reaction, the mixture was post-reacted at 120° C. for 2 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 70°C.

4030 g of polyethyleneimine 600 with 40 mol ethylene oxide/mol NH bonds (amine value: 26.9 mg KOH/g; pH of 10% by weight aqueous solution: 10.8; viscosity (70° C.): 410 mPas) were obtained as a beige solid.

d) PEI600+40EO/NH, quaternized with dimethyl sulfate 25%

1700.0 g of the product from example 1 c) were heated to 70-75° C. under a constant flow of nitrogen in a 2 L reaction vessel. 25.7 g of dimethyl sulfate were added within 15 minutes. The reaction mixture was stirred for an additional 2 hours at 75 °C.

1725.0 g of a beige solid were obtained (amine number: 19.6 mg KOH/g; pH of 10% by weight aqueous solution: 9.4; viscosity (70° C.): 444 mPas).

Embodiment 2: Synthetic 25% quaternized PEI600 EO62

a)PEI600+1EO/NH

1328.5 g of polyethyleneimine 600 (average molecular weight _Mw of 600) and 66.4 g of water were heated to 80° C. and purged 3 times with nitrogen to a pressure of 5 bar in a 3.5 L autoclave. After warming up to 120° C., 1359.4 g of ethylene oxide were added portionwise to 7 bar. To complete the reaction, the mixture was post-reacted at 120° C. for 2 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 70°C. The temperature was raised to 90-110°C and the mixture was dehydrated under vacuum for 2 hours.

2688.0 g of polyethyleneimine 600 with 1 mol ethylene oxide/mol NH were obtained as a yellow viscous oil (amine value: 549 mg KOH/g; pH of 1% by weight aqueous solution: 11.06).

b)PEI600+10EO/NH

704.5 g of the product obtained in Example 1 a) and 21.1 g of a 50% by weight aqueous potassium hydroxide solution were heated to 80° C. in a 5 L autoclave and purged 3 times with nitrogen. The mixture was dehydrated for 2 hours at 120° C. and a vacuum of 10 mbar. After the vacuum was removed with nitrogen, the temperature was raised to 145° C. and 3206.7 g of ethylene oxide were added portionwise to 7 bar. To complete the reaction, the mixture was post-reacted at 120° C. for 2 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 70°C.

3968.0 g of polyethyleneimine 600 (amine value: 101.5 mg KOH/g; pH of 10% by weight aqueous solution: 11.6) were obtained as a yellow-brown viscous liquid with 10 mol ethylene oxide/mol NH bonds.

c)PEI600+62EO/NH

247.8 g of the product obtained in example 1 b) were heated to 80° C. in a 3.5 L autoclave and purged 3 times with nitrogen. The mixture was dehydrated at 120° C. and a vacuum of 10 mbar for 0.5 hours. After the vacuum was removed with nitrogen, the temperature was raised to 140° C. and 1116.3 g of ethylene oxide were added portionwise to 7 bar. To complete the reaction, the mixture was post-reacted at 120° C. for 5 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 70°C.

1410.0 g of polyethyleneimine 600 having 62 mol ethylene oxide/mol NH bonds (amine value: 18.5 mg KOH/g; pH of 10% by weight aqueous solution: 10.8) were obtained as a beige solid.

d) PEI600+62EO/NH, quaternized with dimethyl sulfate 25%

120.0 g of the product from example 1 c) were heated to 70-75° C. under a constant flow of nitrogen in a 0.25 L reaction vessel. 1.26 g of dimethyl sulfate were added over 15 minutes. The reaction mixture was stirred for an additional 2 hours at 75 °C.

This gave 105.0 g of a beige solid (amine value: 13.44 mg KOH/g; pH of a 10% by weight aqueous solution: 8.8).

Example 3: Synthesis of 25% quaternized PEI600EO72

a)PEI600+72EO/NH

232.0 g of the product obtained in example 1 b) were heated to 80° C. in a 3.5 L autoclave and purged 3 times with nitrogen. The mixture was dehydrated at 120° C. and a vacuum of 10 mbar for 0.5 hours. After the vacuum was removed with nitrogen, the temperature was raised to 140° C. and 1254.5 g of ethylene oxide were added portionwise to 7 bar. To complete the reaction, the mixture was post-reacted at 120° C. for 5 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 70°C.

1500.0 g of polyethyleneimine 600 having 72 mol ethylene oxide/mol NH bonds (amine value: 16.27 mg KOH/g; pH of 10% by weight aqueous solution: 10.0) were obtained as a beige solid.

b) PEI600+72EO/NH, quaternized with dimethyl sulfate 25%

120.0 g of the product from example 2a) were heated to 70-75° C. under a constant flow of nitrogen in a 0.25 L reaction vessel. 1.10 g of dimethyl sulfate were added over 15 minutes. The reaction mixture was stirred for an additional 2 hours at 75 °C.

107.0 g of a beige solid were obtained (amine value: 12.3 mg KOH/g; pH of a 10% by weight aqueous solution: 8.9).

Test Methods

Molecular weight determination:

Molecular weights were obtained by using GPC columns arranged in series HEMA Bio linear, 40 8 mm 10 μm, HEMA Bio 100, 300 8 mm, 10 μm, HEMA Bio 1000, 300 8 mm, 10 μm and HEMA Bio 10000, 300 8 mm, 10 μm (by PSS Polymer Standards Service GmbH, Mainz, Germany) Gel Permeation Chromatography (GPC) as weight average molecular weight (M _w ). The eluent is 1.5% formic acid aqueous solution, the flow rate is 1 ml/min, the injection volume is 20 μl, and the sample concentration is 1%. The method was calibrated with a pullulan standard (MW 342-1660000 g/mol, obtained from PSSPolymer Standards Service GmbH, Mainz, Germany).

Instructions

In the method aspects of the present invention, dirty pots are contacted with an effective amount, usually about 0.5-20 ml (per 25 pots to be treated), preferably about 3-10 ml, of a liquid detergent composition of the present invention diluted in water. The actual amount used for a liquid detergent composition is based on the judgment of the user and generally depends on factors such as the specific product formulation of the composition - including the concentration of active ingredients in the composition, the number of dirty bowls to be cleaned, the degree of soiling on the bowls, etc. factor. The particular product formulation in turn depends on many factors such as the target market for the composition product (ie US, Europe, Japan, etc.). Suitable examples can be seen in Table I below.

Usually about 0.01-150ml, preferably about 3-40ml of the liquid detergent composition of the present invention and about 2000-20000ml, more typically about 5000-15000ml of water in a capacity of about 1000-20000ml, more typically about 5000- Combined in a 15000ml tank. The dirty pots are dipped in a sink containing the thus obtained diluted composition, in which the soiled surfaces of the pots come into contact with a rag, sponge or similar article to clean them. The wipe, sponge, or similar article may be soaked in the detergent composition and water mixture and is typically in contact with the basin surface for a period of about 1-10 seconds prior to contacting the basin surface, although the actual time varies with each application and user . Contact of the wipe, sponge or similar article with the surface of the basin is preferably accompanied by simultaneous scrubbing of the surface of the basin.

Another method of use involves immersing the dirty basin in a water bath or keeping it under running water without any liquid dishwashing detergent. The liquid dishwashing detergent absorbing device, such as a sponge, is placed directly into a divided amount of the undiluted liquid dishwashing composition for a period of contact usually of about 1-5 seconds. The absorbent means, and thus the undiluted liquid dishwashing composition, are then each contacted with each soiled dish surface to remove said soils. The absorbent device is typically in contact with the surface of each basin for a period of about 1-10 seconds, although the actual application time depends on factors such as the degree of soiling of the basin. Contact of the absorbent means with the basin surface is preferably accompanied by simultaneous brushing.

Gloss Test Method

The formulation to be tested was diluted with tap water (water hardness: 15 gpg, temperature: 40° C.) to obtain a 10% solution of the original formulation. The solution was applied to 3 drinking glasses by sponge and then rinsed for 10 seconds under running water (water hardness: 15 gpg; temperature: 40°C). After rinsing the glasses were stored vertically and allowed to dry at ambient temperature (20°C). Glasses were scored visually after drying by two judgments for gloss on a 0-6 scale (0 = no streaks/spots at all; 6 = very bad streaks/spots).

Viscosity Test Method

The viscosity of the compositions of the present invention is measured at 20°C on a Brookfield viscometer model #LVDVII+. The spindle used for these measurements is S31, measuring products of different viscosities at an appropriate speed; for example 12rpm for measuring products with a viscosity greater than 1000cps; 30rpm for measuring products with a viscosity of 500-1000cps; 60rpm for measuring products with a viscosity of less than 500cps .

Application example

Examples of hand washing dishes

Table 1 illustrates the preparation of known liquid cleaning compositions. This composition was prepared to illustrate the gloss benefit obtained in hand dishwashing by the incorporation of specific polyethyleneimine structures as shown in Table 2.

Table 1: Cleaning composition prior to addition of alkoxylated polyethyleneimine

*The number of carbon atoms in the alkyl chain is 12-13 and x is 0.5-2.

Ethylan is a nonionic surfactant based on synthetic primary alcohols, commercially available from AkzoNobel.

TO 7 is a nonionic surfactant prepared from saturated iso-C _alcohols .

The solvent is ethanol.

The amine oxide is cocodimethylamine oxide.

1 Glutamic acid-N,N-diacetic acid

2 Diethylenetriaminepentamethylphosphonic acid

**Examples may have other optional ingredients such as dyes, opacifiers, fragrances, preservatives, hydrotropes, processing aids, salts, stabilizers, and the like.

Table 2 illustrates a series of compositions for the gloss prepared and tested. The base formulation for all compositions was formulation I from Table 1 above. With the exception of the control sample (2A), each composition contained 0.1% of an ethoxylated polyethyleneimine having the characteristics specified in the table. Gloss testing was performed according to the method disclosed above. All compositions provide good cleaning. Compositions 2A, 2B, 2C and 2D did not provide good gloss. Compositions 2E-2I provided good gloss results.

Table 2: Gloss Benefits of Incorporating Selected Modified Polyethylenimines into Cleaning Compositions

2A (control) 2B 2C 2D 2E 2F 2G 2H 2I % Formulation I 100% 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% %PEI 0% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% PEI performance -PEI skeleton MW - 600 600 600 600 600 600 600 600 -EO replaced - twenty four 20 30 30 30 50 50 50 -PO replaced - 16 0 0 0 0 0 0 -% quaternization - 0 8% 10% 25% 50% 10% 25% 50% result Gloss level 4.0 3.0 2.0 2.0 1.2 1.5 1.2 1.0 1.0

Table 3 illustrates another series of compositions that were prepared and tested for gloss. The base formulation for all compositions was formulation I from Table 1 above. With the exception of the control sample (3A), each composition contained 0.1% of an ethoxylated polyethyleneimine having the characteristics specified in the table. Gloss testing was performed according to the method disclosed above. Compositions 3B, 3C, 3D and 3E contained a PEI structure that did not provide good gloss results. In contrast, composition 3F exhibits the preferred embodiment of the invention and is especially good in gloss with a degree of ethoxylation of 40% and quaternization of 27%.

Table 3: Gloss Benefits of Incorporating Selected Polyethylenimines into Cleaning Compositions

3A (control) 3B 3C 3D 3E 3F % Formulation I 100% 99.9% 99.9% 99.9% 99.9% 99.9% %PEI 0% 0.1% 0.1% 0.1% 0.1% 0.1% PEI performance -PEI skeleton MW - 600 600 600 600 600 -EO replaces * - 10 10 10 10 40 -PO replaced** - 16 16 16 16 0 -% quaternization - twenty four% 48% 73% 90% 27% result Gloss level 2.7 3.0 2.25 2.5 2.2 1.0

* moles of ethylene oxide per mole of NH

**Moles of propylene oxide per mole of NH

Table 4 illustrates another series of compositions that were prepared and tested for gloss. The base formulation for all compositions was formulation I from Table 1 above. With the exception of the control sample (4A), each composition contained 0.1% of an ethoxylated polyethyleneimine having the characteristics specified in the table. Gloss testing was performed according to the method disclosed above. Compositions 4B and 4C contained a PEI structure that did not provide good gloss results. In contrast, compositions 4D-4K show preferred embodiments of the invention and are particularly good especially in terms of gloss.

Table 4: Gloss Benefits of Incorporating Selected Polyethylenimines into Cleaning Compositions

* moles of ethylene oxide per mole of NH

**Moles of propylene oxide per mole of NH

Examples of Hand Dishwashing Detergent Compositions

*The number of carbon atoms in the alkyl chain is 12-13 and x is 0.5-2.

Ethylan is a nonionic surfactant based on synthetic primary alcohols, commercially available from AkzoNobel.

TO 7 is a nonionic surfactant prepared from saturated iso-C _alcohols .

The solvent is ethanol.

The amine oxide is cocodimethylamine oxide.

1 Glutamic acid-N,N-diacetic acid

2 Diethylenetriaminepentamethylphosphonic acid

**Examples may have other optional ingredients such as dyes, opacifiers, fragrances, preservatives, hydrotropes, processing aids, salts, stabilizers, and the like.

Examples of Hard Surface Cleaning Compositions

The following examples further illustrate the invention. These compositions are prepared by admixing the listed ingredients in the listed proportions (% by weight, unless otherwise indicated). The following examples are intended to illustrate compositions useful in the methods of the present invention, but are not necessarily intended to limit or define the scope of the invention.

C _9-11 EO ₅ is a C _9-11 EO ₅ nonionic surfactant commercially available from ICI or Shell. C _12,14 EO ₅ is a C _12,14 EO ₅ nonionic surfactant commercially available from Huls, A&W or Hoechst. C ₁₁ EO ₅ is a C ₁₁ EO ₅ nonionic surfactant. C _12,14 EO ₂₁ is a C _12-14 EO ₂₁ nonionic surfactant. NaPS is sodium paraffin sulfonate commercially available from Huls or Hoechst. NaLAS is sodium linear alkylbenzene sulfonate commercially available from A&W. NaCS is sodium cumene sulfonate commercially available from A&W. AS is a _C12-13 sulfate surfactant commercially available from Sasol olefins and surfactants. C _12-14 AO is a C _12-14 amine oxide surfactant. The C _12-14 betaine is a C _12-14 betaine surfactant.

DMPEG is polyethylene glycol dimethyl ether. HM-HEC is cetyl hydroxyethyl cellulose. Isofol is 2-butyloctanol commercially available from Condea. Isofol 2-Hexyldecanol commercially available from Condea. n-BP is n-butoxypropanol commercially available from Dow Chemicals. IPA is isopropanol. n-BPP is butoxypropoxypropanol commercially available from Dow Chemicals.

Dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40mm" is intended to mean "about 40mm".

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (6)

1. A kind of ethoxylated polyethyleneimine with the general structure of formula (I): wherein n has a value of 40-90, R is selected from hydrogen, C ₁ -C ₄ alkyl and mixtures thereof, E represents a C ₁ -C ₁₂ alkyl moiety, X ^- represents a suitable water-soluble counterion and polyethylene The degree of quaternization of the nitrogen atoms present in the amine backbone is from 1 to 50%. 2. Ethoxylated polyethyleneimine according to claim 1, wherein n has a value of 45-80. 3. Ethoxylated polyethyleneimine according to claim 1, wherein n has a value of 50-80. 4. Ethoxylated polyethyleneimine according to any one of claims 1-3, wherein the polyethyleneimine backbone has a weight average molecular weight of 400-10000 g/mol. 5. The ethoxylated polyalkyleneimine polymer according to any one of claims 1 to 4, wherein the polyethyleneimine backbone has a weight average molecular weight of 400 to 6000 g/mol. 6. Use of ethoxylated polyalkyleneimine polymers according to any one of claims 1 to 5 in chemical technology applications, car washing, cosmetics, paper and cardboard manufacture, leather and textile industries.